In order to analyze the thermal decomposition of MT based pyrolant in nitrogen and air environments,the thermal analysis experiments of MT and MTV pyrolants were carried out by TG-DTA and DSC.The results show that,in ...In order to analyze the thermal decomposition of MT based pyrolant in nitrogen and air environments,the thermal analysis experiments of MT and MTV pyrolants were carried out by TG-DTA and DSC.The results show that,in nitrogen environment,the spectrum result of Grignard-type reaction~[6] is verified by the decomposition characteristics of MT and MTV pyrolants.8.71% of Mg is consumed in the intermediate reaction of MT at 500-596 ℃ and the heat release of reaction is 31.93 k J/g.The endothermic decomposition of the intermediate product is at 684-740 ℃.In MTV,the intermediate reaction is at 435-595 ℃ and the heat release of reaction are increased by the addition of fluororubber.The intermediate product degrades at 677-745 ℃.In air environment,the decomposition of MT and MTV show the different reaction mechanism from the nitrogen environment.The presence of oxygen is involved in the reaction of Mg,and inhibits the intermediate reaction process of Mg and PTFE.展开更多
Secondary alcohols bearing both axial and central chirality comprise attractive biological activity and exhibit excellent chiral induction in asymmetric reactions.However,only very limited asymmetric catalytic approac...Secondary alcohols bearing both axial and central chirality comprise attractive biological activity and exhibit excellent chiral induction in asymmetric reactions.However,only very limited asymmetric catalytic approaches were developed for their synthesis.We herein describe visible light-mediated cobalt-catalyzed asymmetric reductive Grignard-type addition of aryl iodides with axially prochiral biaryl dialdehydes leading to the direct construction of axially chiral secondary alcohols.Preliminary mechanistic studies indicate that efficient kinetic recognition of diastereomers might occur for axially prochiral dialdehydes to improve the stereoselectivity,which might open a new avenue for the challenging cascade construction of multiple chiral elements.This protocol features excellent enantio-and diastereoselectivity,green and mild conditions,simple operation,and broad substrate scope,providing a modular platform for the synthesis of secondary axially chiral alcohols.展开更多
基金Sponsored by the National Natural Science Foundation of China(Grant No.51076066)
文摘In order to analyze the thermal decomposition of MT based pyrolant in nitrogen and air environments,the thermal analysis experiments of MT and MTV pyrolants were carried out by TG-DTA and DSC.The results show that,in nitrogen environment,the spectrum result of Grignard-type reaction~[6] is verified by the decomposition characteristics of MT and MTV pyrolants.8.71% of Mg is consumed in the intermediate reaction of MT at 500-596 ℃ and the heat release of reaction is 31.93 k J/g.The endothermic decomposition of the intermediate product is at 684-740 ℃.In MTV,the intermediate reaction is at 435-595 ℃ and the heat release of reaction are increased by the addition of fluororubber.The intermediate product degrades at 677-745 ℃.In air environment,the decomposition of MT and MTV show the different reaction mechanism from the nitrogen environment.The presence of oxygen is involved in the reaction of Mg,and inhibits the intermediate reaction process of Mg and PTFE.
基金Natural Science Foundation of Jilin Province(20230101047JC,YDZJ202201ZYTS338)NSFC(22001157,21831002,22193012,and 22201033)+1 种基金Jilin Educational Committee(JJKH20231295KJ,JJKH20231302KJ)the Fundamental Research Funds for the Central Universities(2412022ZD012,2412022QD016,2412021QD007)for generous financial support.
文摘Secondary alcohols bearing both axial and central chirality comprise attractive biological activity and exhibit excellent chiral induction in asymmetric reactions.However,only very limited asymmetric catalytic approaches were developed for their synthesis.We herein describe visible light-mediated cobalt-catalyzed asymmetric reductive Grignard-type addition of aryl iodides with axially prochiral biaryl dialdehydes leading to the direct construction of axially chiral secondary alcohols.Preliminary mechanistic studies indicate that efficient kinetic recognition of diastereomers might occur for axially prochiral dialdehydes to improve the stereoselectivity,which might open a new avenue for the challenging cascade construction of multiple chiral elements.This protocol features excellent enantio-and diastereoselectivity,green and mild conditions,simple operation,and broad substrate scope,providing a modular platform for the synthesis of secondary axially chiral alcohols.
